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STLCOPCB4069171
AROCLOR
resins and plasticizers for chlorinated rubber
TECHNICAL BULLETIN No. O/PL-311
DSW 305014
"Nothlngeontained herein is to be construed is s recommendation to use any product Inconfliet with any patent. MONSANTO MAKES NO WARRANTIES AS TO THE FITNESS OR MERCHANTABILITY OF ANY PRODUCTS REFERRED TO, no guarantee of satisfactory results from reliance upon con* talned information or recommendations, and disclaims all liability for any resulting loss or damage."
Organic Divisian/800 N. Lindbergh Blvd./St. Louis, Missouri 63166
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TABLE OF CONTENTS
INTRODUCTION............................................................................... 5
NUMBERING AROCLOR COMPOUNDS.................................. 6
PROPERTIES OF CHLORINATED RUBBER
General............................................................................................ 7
Physical.........................................................
7
Chemical Resistance.......................................
7
Electrical. ........
8
Mechanical................................................................................. .. 8
Thermal...................................................................................... 8
Physical-Chemical......................................................................... 8
VISCOSITY TYPES.............................................................. ............. 9
SOLVENT COMPATIBILITY.......................
9
FORMULATION AND PROPERTIES OF CHLORINATED RUBBER............................................................10
Formulations for Aroclor Resins and Plasticizers........................ 10
Properties of Formulated Films................................................ .10
APPLICATIONS.....................
12
Alkali-Resistant Coatings.............................................................. 12
Chemical-Resistant Finishes.......................................................... 13
Continuous Metal-Painting Process..............................................14
Marine Finishes............................................................
14
Emulsion Paints..............................................................................15
Mastics............................................................................................. 15
Paper and Textile Coatings.................
16
Adhesives........................................................................................ 16
Electrical Coatings..........................................................................16
Printing Inks......... ......................................................................... 16
OTHER MONSANTOTM PLASTICIZERS FOR CHLORINATED RUBBER...................................
17
TOXICITY AND SAFE HANDLING............................
18
SHIPPING.................
19
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AROCLOR RESINS AND PLASTICIZERS FOR CHLORINATED RUBBER
Some important applications for protective and decorative chlorinatedrubber-based coatings plasticized with Aroclor compounds--
Wood and metal on yachts, barges, and other marine craft
Structural steel for bridges, buildings, roofs, and powerlines
Structural materials at chemical plants, pulp-and-paper mills, textile mills, petroleum refineries, and gas works for protection against acid fumes, alkalies, and gas
Tank cars and other railroad equipment and construction machin ery for protection against corrosive materials and weathering
Equipment and stop-off lacquers used in electroplating
Masonry floors and walls, concrete swimming pools, and high
way markings
'
Cable coatings requiring flame retardance, chemical resistance, and excellent electrical properties
Textile coatings resistant to chemicals, flame, and water
Food-processing buildings
Flame-retardant finishes
Important properties imparted to chlorinated-rubber coatings by Aroclor plasticizers and resin extenders--
Chemical Resistance
Corrosion Resistance
Adhesivity
.
Flame Retardance
Flexibility
Electrical Resistance
Weather Resistance
Nonoxidation
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INTRODUCTION Monsanto's Aroclor chlorinated biphenyls and chlorinated terphenyls are used as plasticizers and resins for chlorinated-rubber-based lac quers, varnishes, and paints. These protective coatings are flame retardant, corrosion resistant, chemical resistant (to acids, alkalies, and water), and have good electrical insulating properties. When properly pigmented, these coatings have unusually good weatherability. Chlorinated-rubber films plasticized with an Aroclor compound grip common structural materials in strong adhesive bonds, and the addition of an Aroclor compound improves the flexibility and life of chlorinated-rubber coatings. The formulations suggested in this bulletin are common in commer cial practice. They are given as starting points or guides for develop ment of new formulations that capitalize on the outstanding qualities of these compounds. .
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NUMBERING AROCLOR COMPOUNDS
The first two digits of the number of an Aroclor compound represent its molecular type, as:
12--chlorinated biphenyls 25---blend of chlorinated biphenyls and chlorinated terphenyls 44--blend of chlorinated biphenyls and chlorinated terphenyls 54--chlorinated terphenyls
The last two digits indicate the weight percentage of chlorine in the product. For example:
Aroclor 1248 is a chlorinated biphenyl that contains 48-weight-per cent chlorine Aroclor 4465 is a 60 biphenyl: 40 terphenyl mixture chlorinated to 65-per cent chlorine Aroclor 5460 is a chlorinated terphenyl with 60-weight-per cent chlorine
The physical properties of the Aroclor plasticizers vary gradually with the degree of chlorination. Compounds with low percentages of chlo rine, such as Aroclor 1221 and 1232, are clear and very fluid. Aroclor 1242, with 42-per cent chlorine, resembles vegetable oil; the product with 48-per cent chlorine is slightly more viscous and looks like a medium-grade mineral oil. At 54-per cent chlorine, the compound is quite viscous. At higher chlorine percentages, the chlorinated biphenyls become gumlike. At 68-per cent chlorine, the range is complete; Aroclor 1268 is a white powder. Both chlorinated terphenyls (Aroclor 5442 and 5460) are yellow solids.
The gradual change in physical properties often allows a processor to select a plasticizer particularly suited for his operation. If a dry mix is desired, Aroclor 1268 acts as a flame retarding filler. It is also pos sible to use it as a solvent-plasticizer at higher processing temperatures. Complete physical properties and specifications for the Aroclor com pounds are listed in technical bulletin O/PL-306, "Aroclor Plasticizers."
PROPERTIES OF CHLORINATED RUBBER
Chlorinated-rubber-based coatings are used extensively for resistance to corrosion, moisture, fungus, mold, and other destructive agents.
Parlon* chlorinated rubber is a mixture of two polymers, with an average chlorine content of 67 per cent, made by chlorination of natural rubber. Its typical properties, according to the manufacturer, Hercules Inc., Wilmington, Delaware, are listed in Table I:
Trademark of Hercules, Inc.
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TABLE 1 -- Typical Properties of Chlorinated Rubber
General
Form as shipped..................... Color of film............................ Odor......................................... Clarity of film....................... , Taste......... ,............................ Moisture, per cent, as shipped
White, granular powder Water white None Good None 0.5 Maximum
Physical
Specific gravity. ........................ Specific volume, as shipped,
cubic inches per pound......... . Bulking value, gallons per pound Refractive Index, at 25C.........
1.64
16.9 0.0735 1.554
Chemical Resistance to:
Acids, weak...............
excellent
Acids, strong............................................
excellent
Alkalies, weak.....................................................excellent
Alkalies, strong...................................................excellent
Salt spray...........................................................good
Alcohols...............................................................excellent
Ketones.............................................................. soluble
Esters................................................................. soluble
Hydrocarbons, aromatic...................................soluble
Hydrocarbons, aliphatic................................... good
Oils, mineral............................................. ......... good
Oils, animal....................................................... poor
Oils, vegetable................................................... poor
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Electrical (clear, unplasticized film*)
Specific surface resistance, ohms x 1010..... 2000 Dielectric strength, volts per mil
(ASTM method)........................................2300 Dielectric constant at 25C and 1000 cycles. .3.1 Power factor at 25C and 1000 cycles..... .0.0015 to 0.0030 Power factor at 25C and 1000 cycles, after
immersion in water for 140 hours and surface wiped dry...................................... 0.0027
Mechanical (clear, unplasticized film*)
20-cp. type
Tensile strength, dry, pounds per square inch......................................... . . . .4270
Tensile strength, wet, pounds per . square inch......................................... ....4100
Elongation, dry, per cent...................... . . . .3.6
Elongation, wet, per cent..................... ... .3.8
Modulus of elasticity, pounds per square inch......................................... . .. .1.4 x 106
Hardness, Sward index, per cent of glass.. .90
1000-C'i type
4850
4360 3.3 3.4
....
Note: Flexibility of Parlon film increases with viscosity of Parlon used.
Thermal (clear, unplasticized film*)
Burning rate...................................................nonflammable Effect of dry heat on film.............................stable at 125C Softening point, C........................................decomposes at 135 to 150
Physical-Chemical (clear, unplasticized film*)
Effect of sunlight.......................................... Discolors and embrittles Effect of aging................................................Very slight Effect of hot water.........................................Blushes Effect of cold water...................................... None Moisture absorption (80% relative
humidity for 24 hours), per cent..............0.27 Moisture-vapor permeability of 0.003-inch
film (grams water/square centimeter/0.01 centimeter/hour at 21C)......................... 0.2 x 104
laid down from toluene solution
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VISCOSITY TYPES
TABLE 2 -- Parlon Viscosity Types
Viscosity Type 5 cp...
10 cp... 20 cp... 125 cp... 1000 cp...
Viscosity Range (centipoises) 5 to 7 B to 12
16 to 25 110 to 190 800 to 2000
Examples of actual or suggested applications of the several viscosity types are as follows:
Type 5 cp.
10 cp.
20 cp.
125 cp.
1000 cp.
Example of Use
In printing inks and as a fortifier for alkyd resin enamels In high-solid finishes and as a fortifier for alkyd resin and
oleoresinous varnishes and enamels
As a film-former in protective coatings and as a fortifier in enamels and varnishes
As a film-former in protective coatings, in paper lacquers, adhesives, and textile finishes
As a film-former in adhesives, textile finishes, and other finishes where flexibility is important
SOLVENT COMPATIBILITY
Solvents and solvent mixtures suggested for use in preparing formula tions with Aroclor and Parlon are given in Table 3:
TABLE 3 -- Suggested Solvents for Compositions with Aroclor and Parlon
Amsco Solv B and E Amyl acetate Butyl acetate Carbon tetrachloride Cellosolve6 Diacetone alcohol Diethyl carbonate Ethyl acetate Ethylene dichloride High-Flash naphtha Methyl acetate Methyl ethyl ketone
Methyl isobutyl ketone Methyl salicylate Mobilsol' Nos. 74, 75 NotoU Octyl acetate Solvesso' 100 Tollac* Toluene Trichloroethylene Union' Aromatic Solvent 3553-10 Union Solvent No. 30 Xylene
a) Trademark of American Mineral Spirits Co. b) Trademark of Union Carbide Chemical Co. c) Trademark of Socony Mobil Oil Co.
d) Trademark of Neville Chemical Co. e) Trademark of Esso Standard Oil Co. I) Trademark of Union Oil Co.
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FORMULATIONS AND PROPERTIES OF CHLORINATED RUBBER
Chlorinated-Rubber Films
Chlorinated rubber is very hard & brittle; consequently plasticizers and plasticizing resins must be added to make useful coatings. To make chemical- and corrosion-resistant coatings, the modifiers must likewise be nonreactive with acids, alkalies, and salts. As little as five per cent of a saponifiable material, such as linseed oil, alkyd resin, or ester plasticizer, seriously detracts from the alkali resistance of the finished coating. Monsanto compounds, such as Aroclor 5460 and Aroclor 1254 or 1260, are the best available plasticizing resin and plasticizers, respectively, since they are unaffected by acids, alkalies, or salts. The following table summarizes some of the benefits imparted to chlorinated rubber coatings by Aroclor plasticizers:
TABLE 4 -- Benefits of Aroclor Plasticizers In Chlorinated Rubber
GOOD ADHESION TO
RESISTANCE TO
Alum Aroclor inum Steel Transite
Cello phane
10% 5%
Cold-
Hydro- Sodium Sodium
Sward Check
chloric Hydrox- Chlor-
Hard Resist
Acid ide ide Water ness ance
1254 -- -- X
X XX
X X 35 3
1260 -- --
X
X XXX X 40 4
5460 X X X -- XXX X 22 2
Aroclor 1262 and 5460, resinous types, show good compatibility in chlorinated-rubber films laid down from toluene solution containing 20-per cent of the plastic in ratios of 2:1 and 1:1 (Parlon to Aroclor). The plasticizer types, Aroclor 1252, 1254, and 1260, also have good compatibility. Formulations and properties of films derived from both resin- and plasticizer-type Aroclor are listed in Table 5:
TABLE 5 -- Formulations Containing Aroclor Resins or Plasticizers
Ingredient
Parts by Weight
Parlon, 20-cp........................16 16 16 12 12' 12
Aroclor 5460....................... 8 8 8 12 12 12
Aroclor 1254 or 1260............... -- -- -- -- -- --
Dibutyl phthalate................... -- 4 -- -- 3 --
Tung oil, Thermolyzed, 976....-- -- 5 -- -- 3.75
Xylene or butyl acetate...........76 72 71 76 73 72.25
20 20 20 - ---- 4 7 20 -- ---- ------ 76 73 70
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The Aroclor compounds impart the following advantages to the films cast from these lacquers:
Adhesion
Unplasticized chlorinated-rubber films have very poor adhesion. The lacquer film containing Aroclor 5460 adheres well to aluminum, bare steel, primed steel, galvanized iron, and Transite surfaces. The lacquer films plasticized with Aroclor 1254 or 1260 give good adhesion to Trans ite, cellophane, galvanized iron, and primed-steel surfaces.
Though compounds with an Aroclor alone possess pronounced adhe sion qualities, better adhesion to all of the surfaces results if mixtures of Aroclor or varied contents are used.
Resistance to Aqueous Solutions
Chlorinated-rubber films with Aroclor 1254 or 1260 (plasticizers) and Aroclor 5460 (resin) show satisfactory resistance to solutions of 10-per cent hydrochloric acid, 5-per cent sodium hydroxide, 5-per cent sodium chloride, and water-spot tests.
Film Hardness
Softer films are produced with Aroclor 5460 in ratios of 5:10 and 10:10 (Aroclor and Parlon) than with other commercial resins in similar mixtures. Likewise, softer films result from Aroclor 1254 or 1260 in ratios of 2:10 and 5:10 (Aroclor and Parlon) than with other com mercial plasticizers at these concentrations. These tests show that Aroclor compounds have strong plasticizing action on chlorinated rubber.
Cold-Check Resistance
Aroclor 5460 is superior to phenol-formaldehyde resins in cold-check resistance imparted to chlorinated-rubber films, but not as good as long-oil-alkyd modification. Aroclor 1260 is a somewhat better plasti cizer than Aroclor 1254.
Weather Resistance
Pigmented chlorinated-rubber finishes containing Aroclor have con sistently withstood outdoor weather tests, but unpigmented finishes do not weather well regardless of the resin or plasticizer used.
Poor resistance to ultraviolet light is also a weakness of chlorinated rubber. Most pigments (except ultramarine blue) are usable with Parlon and are recommended if the coating is to be subjected to outdoor weather or ultraviolet light. However, pigment protection varies con siderably. Inspection of alkyd enamels fortified with Parlon showed weatherability varied from 63 months with chrome green to 4 months for titanium dioxide-iron blue combinations.
Sanding and Polishing Properties
Plastic films compounded with Parlon and Aroclor 5460, 1254, or 1260 have showed satisfactory sanding and polishing characteristics.
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APPLICATIONS
Alkali-Resistant Coatings
Products containing Aroclor and chlorinated rubber are highly resist ant to alkalies and moisture. Paints with combinations of Aroclor and chlorinated rubber are used in large quantities for concrete floors, walls, swimming pools, and other surfaces. Paint formulations are sug gested in Table 6:
TABLE 6 -- Paints for Alkaline Surfaces
Ingredients Parlon (20-cp.) chlorinated rubber Medium-oil, drying alkyd resin Long-oil, drying alkyd resin Aroclor 1254 Aroclor 5460 Titanium Dioxide Zinc Oxide Silica Flour Carbon Black Magnesium Silicate Bentone* 34 gelling agent Epichlorohydrin Xylene Hi-Flash naphtha Turpentine Solvesso 100 Solvesso 150
Basement Floors (parts) 100
45 55
89 11 17 1
12
239
-..
Fed-Spec. TT-P-91 (parts)
100
56 33 89 11
3
12
26
237
Concrete Swimming
Pool (parts)
100 50
50
112
115 13 1
450
90
trademark of National Laad Co.
#
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Chemical-Resistant Finishes
Particular care is necessary in choosing resins and plasticizers for chemi cal-resistant paints. Chlorinated-rubber formulations with an Aroclor plasticizer have proved outstanding for acid and alkali resistance. Five suggested formulations are shown in Table 7.
TABLE 7 -- Formulations for Chemical-Resistant Paints
Ingredients
Parlon, (20-cp.) chlorinated rubber
Phenolic resin
-
Alkyd resin
Aroclor 1254
Aroclor 1260
Aroclor 5460
Tung oil, Thermolyzed, 976
Iron oxide
Titanium dioxide
Zinc oxide
Epichlorohydrin
Stabilizer
Xylene
Toluene
Solvesso 100
Hi-Flash naphtha
Turpentine
Exterior* use, acids
(parts)
Exterior6
use, alkalies (parts)
Interior* use,
acids and alkalies (parts)
Maximum'2 resistance, acids and
alkalies (parts)
Soap resistant (parts)
100 100 100 100 100
40
40
30 30 50 45
33
40 50
30 30
64
100 100 100 100
150
50
0.5
5
325 325 330
245
100
250
86
28
These formulations were applied to metal bars or panels and tested for resistance:
a) Excellent outdoor protection to metal surfaces in acid-manufacturing plants b) Good performance on exteriors of alkali-producing plants c) Good resistance to 10-per cent hydrochloric acid and 5-per cent sodium hydroxide solutions d) Excellent resistance to Kids, alkalies, and salt solutions (Also adhered well to glass and other surfaces) e) Good resistance to warm, soapy water Note: No finishes with an Aroclor compound or chlorinated rubber are recommended for continuous exposure at temperatures above 140 F.
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Continuous Metal-Painting Process
A recently-developed continuous-painting process for finishing metal offers savings on capital investment, plant space, and operating costs. The technique utilizes the physical properties of trichloroethylene, the only solvent in the paint. Metal parts enter the unit covered with grease and leave the other end completely painted and dry to the touch. Detailed information about the process can be obtained from E. I. DuPont de Nemours & Co., Inc., Wilmington, Delaware. The formulation in Table 8 has given good characteristics in this con tinuous-painting system:
TABLE 8 -- Formulation for Continuous-Painting Process
Ingredients Parlon (20-cp) chlorinated rubber Long-oil, drying, alkyd resin Aroclor 1254 Titanium Dioxide (Rutile) Bentone 38 gelling agent Epoxy stabilizer Trichloroethylene
Parts by Weight
Pigment0
Vehicle
Dispersion
100
15 23.7
50
100
1.25*
3.9
217 53.5
a) Add pigment dispersion to vehicle after 24 hours in pebble mill b) Add gelling agent to pigment dispersion during last two h&rrs of grind
Marine Finishes
The marine industry makes great use of chlorinated-rubber coatings plasticized with Aroclor compounds to protect wood and metal on boats, barges, and other marine equipment. They resist salt water, and their hard finish deters algae and other marine growth. A suggested formula for a white marine paint is given in Table 9:
TABLE 9 -- Formulation for a White Marine Paint
Ingredients Parlon (20-cp) chlorinated rubber Long-oil, oxidizing, alkyd resin Aroclor 1254 Titanium dioxide Xylene Hi-Flash Naphtha
Parts by Weight 77 23 23 96.5 87.5 77
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Emulsion Paints
If chemical resistance is required on porous surfaces, Aroclor 1254 is often added to chlorinated-rubber-emulsion paints. Hercules Powder Company reports that preferred water phases for such paints are either a 1-per cent-distilled-water solution of Aerosol * OT or a 4-per-cent-distilled-water solution of sodium oleate. A lacquer-to-water weight ratio of 2.5 to 1 is suggested for the complete emulsion. Chlorinated rubber of any viscosity may be used. A typical lacquer phase for such an emulsion paint is given in Table 10:
TABLE 10 -- Formulation for Lacquer Phase of Emulsion Paint
Ingredients Parlon chlorinated rubber Aroclor 1254 Aroclor 5460 Xylene Hi-Flash naphtha
Parts by Weight 28 14 10 24 24
Mastics
Mastic compositions are used to deposit thick films with a minimum m number of coats. Mastics modified with Aroclor compounds can ef
fectively seal cracks in concrete, smooth rough concrete surfaces for subsequent glossy coatings, give excellent corrosion resistance under severe conditions, and retard fire. A typical starting formulation is given in Table 11:
TABLE 11 -- Mastic Composition
Ingredients Parlon (20-cp) chlorinated rubber Aroclor 1254 Aroclor 5460 Asbestos Titanium Dioxide (Rutile) Toluene
Parts by Weight 100 30 49 160 25 300
Although this mastic formulation adheres well to either wood or masonry, a primer is suggested before application to steel. To further increase fire retardance, replacement of 33 parts of the asbestos by 47 parts of antimony oxide is suggested as a starting formulation.
'Trademark of American Cyanamid Co.
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Paper and Textile Coatings
Chlorinated-rubber coatings with Aroclor plasticizers are worthy of consideration for specific end uses on paper and textiles, although they are generally restricted by odor. Unpigmented finishes are suitable for certain fabrics used indoors, but not for exposure to high temperatures or direct sunlight.
Adhesives
Chlorinated-rubber adhesives with an Aroclor plasticizer were de veloped originally for acid-bottle labels because of their general re sistance to chemicals. These adhesives are also of unusual interest because they are flame resistant. A typical formulation is given in Table 12:
TABLE 12 -- Formulation for Acid- and Flame-Resistant Adhesive
Ingredients Parlon (125-cp.) chlorinated rubber Aroclor 1254 Aroclor 1260 Toluene
Parts by Weight 20 6 6 68
Electrical Coatings
Because of their desirable electrical properties, these compositions are useful for insulating and protecting electrical wire and apparatus from moisture. With selected fungistats and waxes, coatings of this type are used to protect electronic equipment in the tropics against moisture and fungi. The fire retardance of Aroclor and Parlon combina tions is an added dividend in the electrical field.
Printing Inks
Printing inks requiring fast drying time and chemical resistance are often based on chlorinated-rubber compositions plasticized with an Aroclor compound. These inks are especially useful on soap wrappers and boxes, bottle labels, and many other commodities because of their alkali resistance.
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OTHER MONSANTO PLASTICIZERS COMPATIBLE WITH CHLORINATED RUBBER
The following Monsanto plasticizers (Table 13) are also compatible with chlorinated rubber, but none gives the over-all desired qualities attained by using an Aroclor plasticizer:
TABLE 13 -- Other MonsantoTM Plasticizers Compatible With Chlorinated Rubber
Dibutyl phthalate Diethyl phthalate Dimethyl phthalate Santicizer B-16 plasticizer
Santicizer M-17 Santolite MHP plasticizer Tricresyl phosphate Triphenyl phosphate
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